CN103641682B - Method of preparing glycol by utilization of biomass derivative glycolide - Google Patents
Method of preparing glycol by utilization of biomass derivative glycolide Download PDFInfo
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- CN103641682B CN103641682B CN201310547701.2A CN201310547701A CN103641682B CN 103641682 B CN103641682 B CN 103641682B CN 201310547701 A CN201310547701 A CN 201310547701A CN 103641682 B CN103641682 B CN 103641682B
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- glycollide
- ethylene glycol
- glycol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method of preparing glycol by utilization of biomass derivative glycolide. According to the method, the biomass derivative glycolide is used as a raw material, a metal and a metal oxide are used as catalysts, an active metal elementary substance as a reductant, and the product glycol with high added value is obtained with a yield reaching 94% by reacting in a hydrothermal reactor at 150-300 DEG C for 100-300 min in a sealed condition. The method is capable of synthesizing the glycol with high efficiency and high selectivity, and using the reproducible biomass derivative widespread in nature as the raw material, thus avoiding large fossil fuel consumption in traditional industrial preparation methods. Preparation of complex catalysts is not needed. The operation is simple. Water is used as a hydrogen source and the reaction solvent so that pollution to the environment is small. The conversion rate is high and the method is beneficial to industrial production. The product glycol can be widely used for producing antifreezing agents, cleaning agents, biodegradable polyester fiber and plasticisers, preparing medicines, and the like, and is an important intermediate chemical and solvent.
Description
Technical field
The invention belongs to derived energy chemical technical field, be specifically related to a kind of method utilizing biomass derivatives glycollide to prepare ethylene glycol.
Background technology
In global 20th century of modern paces of entering into in 21 century, fossil oil potential energy starved crisis, particularly from petroleum refining gasoline out, be the reason causing Global Oil crisis.Therefore, reduce the dependence to fossil oil, develop new reproducible clean energy and be subject to people and more and more pay close attention to.The ethylene glycol synthetic method of current domestic and international industrial widespread use is mainly obtained through catalytic hydration by oxyethane, this needs consumption of ethylene resource, and ethene is mainly refined by traditional petroleum resources at present, this technique mainly contains follow-up equipment (vaporizer) long flow path, energy consumption is high, glycol selectivity is on the low side and total recovery only has the shortcoming such as about 70%, therefore seek renewable energy source to replace fossil oil, it is imperative that the novel method of development environment close friend, economy, environmental protection prepares ethylene glycol.Biomass energy is enriched because it has recyclability, low stain, extensive distributivity and total amount, has very large application prospect.
Summary of the invention
A kind of biomass derivatives glycollide that utilizes of novel high-efficient simple is the object of the present invention is to provide to prepare the method for ethylene glycol.The method transformation efficiency is high, good product selectivity, the noble metal catalyst prepared without the need to using complicated difficult, simple to operate, use water as solvent and hydrogen source environmental pollution little, energy consumption is low, is conducive to suitability for industrialized production.Glycol product is a kind of important intermediate chemical and solvent, can be widely used in producing frostproofer, sanitising agent, Biodegradable polyester fiber, fluidizer, pharmacy etc.
The object of the invention is to be achieved through the following technical solutions:
The present invention relates to a kind of method utilizing biomass derivatives glycollide to prepare ethylene glycol, described method comprises the steps:
A, in hydrothermal reactor, add glycollide, catalyzer, reductive agent and water;
B, in described hydrothermal reactor, be filled with nitrogen and seal;
C, described hydrothermal reactor is put into baking oven under 150 ~ 300 DEG C of conditions, react 100 ~ 300min;
After D, reaction terminate, membrane filtration reaction mixture, obtains ethylene glycol.
Preferably, the mol ratio of described glycollide, catalyzer, reductive agent is 0.5:3 ~ 12:10 ~ 30.Be more preferably 0.5:3 ~ 6:25 ~ 30; Most preferably be 0.5:6:25.
Preferably, in described hydrothermal reactor, water filling ratio is 15% ~ 45%.
Preferably, described catalyzer comprises metal or metal oxide powder.
Further preferably, described catalyzer is Cu, Fe, Co, Fe
2o
3, Ni
2o
3, Fe
3o
4, CuO, Co
2o
3or Cu
2o.
Preferably, described reductive agent comprises metal-powder simple substance.
Further preferably, described metal-powder simple substance is Al, Fe, Mg, Mn or Zn.
Preferably, the filter membrane that described filtration is specially employing 0.45 μm filters.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention uses biomass derivatives glycollide to make raw material preparing ethylene glycol, glycollide can be obtained from biomass resource oxyacetic acid (coming from sugarcane that nature extensively exists, beet and immature Sucus Vitis viniferae), without the need to consuming fossil energy, can the partial rcsponse nowadays energy problem that faces of the whole world;
(2) the present invention uses high-temperature high pressure water to make reaction solvent.Compared with ortho-water, the specific inductivity of high-temperature high pressure water reduces, and intermolecular hydrogen bond weakens, and isothermal compressibility improves, ion constant (K
w) almost add 1000 times than normal-temperature water.Utilize these characteristics of high-temperature high pressure water, can realize making reductive agent with metal cheap and easy to get and compound thereof and glycollide is transformed into this high added value organism of ethylene glycol by catalyzer under hydrothermal conditions, realize efficient low-consume and transform organic resource.
(3) the present invention is without the need to additionally passing into high-purity hydrogen, significantly reduces energy consumption of reaction, and environmental protection more, pollution on the environment is little;
(5) the present invention uses metal cheap and easy to get and metal oxide to make catalyzer, without the need to preparing complicated noble metal catalyst;
(6) without the need to adding alkali;
(7) ethylene glycol productive rate of the present invention can reach 94%, and selectivity is good, and byproduct of reaction is few.
Accompanying drawing explanation
By reading the detailed description done non-limiting example with reference to the following drawings, other features, objects and advantages of the present invention will become more obvious:
Fig. 1 is the GC/MS spectrogram of the product of embodiment 1;
Fig. 2 is the GC-FID spectrogram of the product of embodiment 1.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
embodiment 1
The method that the present embodiment relates to a kind of metal simple-substance (Zn powder), metal oxide (CuO powder) hydrothermal conversion glycollide prepares ethylene glycol, reaction equation is as follows:
Described method comprises the steps:
Successively glycollide (0.5mmol), Zn powder (25mmol) and CuO powder (6mmol) are loaded in the hydrothermal reactor of Teflon liner, add water and make reactor filling ratio be 25%, seal be filled with the interference of nitrogen excluding air in reactor after, reactor being put into baking oven makes its temperature of reaction be 250 DEG C, reaction times 150min, takes out mixture and filters to obtain ethylene glycol after reaction.
Carry out qualitative (see Fig. 1) and FID quantitative analysis (see Fig. 2) by after reaction to product GC/MS, GC/MS qualitative analysis shows, ethylene glycol is primary product, and FID quantitative analysis shows, productive rate reaches as high as 93.9%.Industrial application adopts suitable hydrothermal reactor by demand, and can control temperature of reaction is 150 ~ 300 DEG C, and water filling ratio, 15% ~ 45%, reacts 100 ~ 300min.By this reaction, glycollide can be converted into ethylene glycol in a large number, easy to operation and selectivity good.
Wherein, the metal simple-substance and the residual metallic compound that react generation under hydrothermal condition can be recovered or do other production purposes, thus reduce the pollutant component entering environment to a certain extent.
embodiment 2
The method that the present embodiment relates to a kind of metal simple-substance (Zn powder), metal oxide (CuO powder) hydrothermal conversion glycollide prepares ethylene glycol, described method comprises the steps:
Successively glycollide (0.5mmol), Zn powder (25mmol) and CuO powder (6mmol) are loaded in the hydrothermal reactor of Teflon liner, add water and make reactor filling ratio be 25%, seal be filled with the interference of nitrogen excluding air in reactor after, reactor being put into baking oven makes its temperature of reaction be 250 DEG C, reaction times 200min, takes out mixture and filters to obtain ethylene glycol after reaction.
Carry out qualitative and FID quantitative analysis by after reaction to product GC/MS, GC/MS qualitative analysis shows, ethylene glycol is primary product, and FID quantitative analysis shows, productive rate reaches as high as 90.2%.Industrial application adopts suitable hydrothermal reactor by demand, and can control temperature of reaction is 150 ~ 300 DEG C, and water filling ratio, 15% ~ 45%, reacts 100 ~ 300min.
Wherein, the metal simple-substance and the residual metallic compound that react generation under hydrothermal condition can be recovered or do other production purposes, thus reduce the pollutant component entering environment to a certain extent.
embodiment 3
The method that the present embodiment relates to a kind of metal simple-substance (Zn powder), metal oxide (CuO powder) hydrothermal conversion glycollide prepares ethylene glycol, described method comprises the steps:
Successively glycollide (0.5mmol), Zn powder (30mmol) and CuO powder (6mmol) are loaded in the hydrothermal reactor of Teflon liner, add water and make reactor filling ratio be 25%, seal be filled with the interference of nitrogen excluding air in reactor after, reactor being put into baking oven makes its temperature of reaction be 250 DEG C, reaction times 150min, takes out mixture and filters to obtain ethylene glycol after reaction.
Carry out qualitative and FID quantitative analysis by after reaction to product GC/MS, GC/MS qualitative analysis shows, ethylene glycol is primary product, and FID quantitative analysis shows, productive rate reaches as high as 92.5%.Industrial application adopts suitable hydrothermal reactor by demand, and can control temperature of reaction is 150 ~ 300 DEG C, and water filling ratio, 15% ~ 45%, reacts 100 ~ 300min.
Wherein, the metal simple-substance and the residual metallic compound that react generation under hydrothermal condition can be recovered or do other production purposes, thus reduce the pollutant component entering environment to a certain extent.
embodiment 4
The method that the present embodiment relates to a kind of metal simple-substance (Zn powder), metal simple-substance (CuO powder) hydrothermal conversion glycollide prepares ethylene glycol, described method comprises the steps:
Successively glycollide (0.5mmol), Zn powder (25mmol) and CuO powder (6mmol) are loaded in the hydrothermal reactor of Teflon liner, add water and make reactor filling ratio be 35%, seal be filled with the interference of nitrogen excluding air in reactor after, reactor being put into baking oven makes its temperature of reaction be 250 DEG C, reaction times 150min, takes out mixture and filters to obtain ethylene glycol after reaction.
Carry out qualitative and FID quantitative analysis by after reaction to product GC/MS, GC/MS qualitative analysis shows, ethylene glycol is primary product, and FID quantitative analysis shows, productive rate reaches as high as 87.9%.Industrial application adopts suitable hydrothermal reactor by demand, and can control temperature of reaction is 150 ~ 300 DEG C, and water filling ratio, 15% ~ 45%, reacts 100 ~ 300min.
Wherein, the metal simple-substance and the residual metallic compound that react generation under hydrothermal condition can be recovered or do other production purposes, thus reduce the pollutant component entering environment to a certain extent.
embodiment 5
The present embodiment relates to a kind of metal simple-substance (Zn powder), metal simple-substance (Cu
20 powder) hydrothermal conversion glycollide prepares the method for ethylene glycol, and described method comprises the steps:
Successively by glycollide (0.5mmol), Zn powder (25mmol) and Cu
2o powder (6mmol) loads in the hydrothermal reactor of Teflon liner, add water and make reactor filling ratio be 25%, seal be filled with the interference of nitrogen excluding air in reactor after, reactor being put into baking oven makes its temperature of reaction be 250 DEG C, reaction times 150min, takes out mixture and filters to obtain ethylene glycol after reaction.
Carry out qualitative and FID quantitative analysis by after reaction to product GC/MS, GC/MS qualitative analysis shows, ethylene glycol is primary product, and FID quantitative analysis shows, productive rate reaches as high as 81.7%.Industrial application adopts suitable hydrothermal reactor by demand, and can control temperature of reaction is 150 ~ 300 DEG C, and water filling ratio, 15% ~ 45%, reacts 100 ~ 300min.
Wherein, the metal simple-substance and the residual metallic compound that react generation under hydrothermal condition can be recovered or do other production purposes, thus reduce the pollutant component entering environment to a certain extent.
Above specific embodiments of the invention are described.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.
Claims (4)
1. utilize biomass derivatives glycollide to prepare a method for ethylene glycol, it is characterized in that, described method comprises the steps:
A, in hydrothermal reactor, add glycollide, catalyzer, reductive agent and water;
B, in described hydrothermal reactor, be filled with nitrogen and seal;
C, described hydrothermal reactor is put into baking oven under 150 ~ 300 DEG C of conditions, react 100 ~ 300min;
After D, reaction terminate, filter reaction mixture, obtain ethylene glycol;
Described catalyzer is Cu, CuO or Cu
2o; Described reductive agent is Al, Fe, Mg, Mn or Zn.
2. the method utilizing biomass derivatives glycollide to prepare ethylene glycol according to claim 1, is characterized in that, the mol ratio of described glycollide, catalyzer, reductive agent is 0.5:3 ~ 12:10 ~ 30.
3. the method utilizing biomass derivatives glycollide to prepare ethylene glycol according to claim 1, is characterized in that, in described hydrothermal reactor, water filling ratio is 15% ~ 45%.
4. the method utilizing biomass derivatives glycollide to prepare ethylene glycol according to claim 1, is characterized in that, the filter membrane that described filtration is specially employing 0.45 μm filters.
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|---|---|---|---|
| CN201310547701.2A CN103641682B (en) | 2013-11-06 | 2013-11-06 | Method of preparing glycol by utilization of biomass derivative glycolide |
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|---|---|---|---|
| CN201310547701.2A CN103641682B (en) | 2013-11-06 | 2013-11-06 | Method of preparing glycol by utilization of biomass derivative glycolide |
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| CN103641682A CN103641682A (en) | 2014-03-19 |
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| CN104529706A (en) * | 2014-11-06 | 2015-04-22 | 上海交通大学 | Preparation method of 1,2-propanediol using biomass derivative ethyl lactate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493569A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Method of preparing gamma-butyrolactone and/or 1,4-butanediol using chromium less catalyst |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1493569A (en) * | 2002-10-30 | 2004-05-05 | 中国石油化工股份有限公司 | Method of preparing gamma-butyrolactone and/or 1,4-butanediol using chromium less catalyst |
Non-Patent Citations (2)
| Title |
|---|
| Catalytic Hydrogenation of Carboxamides and Esters by Well-Defined Cp*Ru Complexes Bearing a Protic Amine Ligand;Masato Ito et al.;《Journal of the American Chemical Society》;20110307;第133卷;4240-4242 * |
| Efficient hydrogenation of biomass-derived cyclic di-esters to 1,2-diols;Ekambaram Balaraman et al.;《Chemical Communication》;20111031;第48卷;1111-1113 * |
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Granted publication date: 20150422 Termination date: 20191106 |